Metallizable polyazo dyestuffs and a process for their preparation



Patented Aug. 17 1948 i UNITED, STAT METALLIZABLE POLYAZO DYESTUFFS AN A PROCESS FOR PREPARATION Walter Wehrli and CharlesPetitjean, Basel, Switzerland, assignors to Sandoz Limited, Fribourg,

Switzerland, a Swissfirrn No Drawing. Application June 29,1944, Serial 2 No. 542,810. In Switzerland July 2,1943

The present invention, relates-to new metallizable polyazo dyestufis dyein'g cellulosic fibres in brown shades whose fastness properties can u, be improved by an after-treatment with metallizing agents, and to a process for their manufacture. 2

We have found that thenew metallizable polyazo dyestufis of the general formula wherein Y stands for a member of the group selected from hydrogen and alkyl, and X stands for a diphenyl radical of the benzidine series, can be obtained by coupling 1 mole of resorcinol with 1 mole of a diazotized aminoazo dyestufi of the general formula NH: I

wherein A means the radical of a (haze; dia zoazo z or coupling component, which radical, does. not contain diazotizable amino groups orcarb'on -atoms being capable of coupling, and wherein the benzene nucleus I contains one hydroxy group; in ortho;position .to .the amino groum the other free positions of the benzene nucleusrI severally. carrying a substituent. selected train the class consisting of hydrogen, 'alkyl,1 nitro,

halogen and sulpho groups, and with, 1 molepf an intermediate compound prepared by coupling '1 mole of a tetrazotized 4 :4,'-diami'nodiarylwwith 1 mole of a 1-hydroxybenzene-2-carboxylic acid.

The polyazo dyestuffs of the above formulacan also be obtained by first coupling the resorcino l with 1 mole of the intermediate compolundiip epared from a 4:4'-diaminodia;ryl and a I-ihydroxybenzene-2-carboxylic acid andv subse' quently coupling the diazo dyestuff thus obtained with the diazotized aminoazo, dyestufifof th lotmula NHz

wherein A has the same meaning as above men- 5 Claims. (Cl. 260-144) The raminoaz o dyestuffs of the general formula wherein A and I have the signification as described above and which are required for the preparation of the new metallizable polyazo dyestufi's may .be produced in several ways; Thus, for instance, diazosor diazoazo compounds con- .taining neither. free .nor acylated amino-groups, nbr' carbon" atoms capable of coupling arecoupled with coupla'ble N-acylated l-hydroriy-Z-amino- The new dyestufl prepared accord'ng -to the present process dye cotton and regenerated cellulose fi-bre s in brown shades, the -fastne ssof which can be improved by an after-treatment with metallizing agents. For instance; by the after-treatment with copper yield i'ng compounds an -important improvement of the light-fastness and of thew'et-fastnesses will be reached. 1

The following examples, without being limitative, illustrate the present invention.

Example 1 22.3 parts, of naphthionic acid are diazotized in the usual way and the diazo compound coupled with 15.1 parts of 1-acetylamino-Z-hydroxybenzeneinpresence of 13.3 parts of 30% caustic soda lyje ofwater and of sodiurnrcarbonategThe 'monoazo L'dyestufi's" then precipitated-by means of hydrochloric 'aci'djandi filtered; q The sap'on-i ficati'on i'scar'ried outby hea ingflitwith diluted sm'phurie The lsapbni-fied product is ,then

- filter'edarid Washedl'witl'i water. It possesses the probable'formulai I,

' v ran-Q 011 For further diaz'otization the monoazo dyestufi is dissolved in water in thepres'nce of sodium tioned and wherein the benzene nucleus 1; contains one hydroxy' group in' ortho-position to the amino grou'pand may'contain furtfi'ers'uhstitu ents. -r

hydroxide; '7 parts of sodium nitrite are added to the resulting solution, which, is then cooled down afid'allowedto'run under good stirring "into hydrochloric acid. The diazotization being complete, the coupling is carried out with 11' parts of resorcinol, dissolved in a sodium car- 2,447,222 H 3 4 bonate solution. The diazo dyestufi thus 011- of benzidine and.13.8 parts of salicyclic acid. The tained is precipitated with hydrochloric acid and tetrakisazo dyestufi is finally salted out in the filtered. It is again dissolved in water in the warmth and dried. It possesses the probable forpresence of sodium carbonate and coupled with imula V coon Hols N=N H OH 7 the intermediate compound prepared from 18.4 and dyes cotton in red-brown shades becoming parts of benzidine and 13.8 parts of salicylic brown aftera treatment with copper salts. By acid. The tetrakisazg dyestuif is then precipithis after-treatment the fastness to washing, to tated in the warmth by means of sodium ch10- light as Well as to alkalis becomes largelyimride and filtered. Itcorresponds to the probable 2o proved. V V formula 7, OH

coon

and constitutes, in dry form, a dark powder dye.- Example 3 ing cotton in reddish-brown. shades. By aftertreatment with copper sulphate the dyeings beg; parts of the monoazo dyestufi of the for comevioletish red-brown, the dyeings possessing 011 then largely improved fastness properties t g k washing, to light andto acids. 7

V Example 2 I 1 10, some NH2 22.3 parts of naphthionic acid are diazotized in the usual way and combined with 16.5 parts 01' 1- methyl-3-acetylamino-4-hydroxybenzene in the 40 presence of 13.3 parts of 30% caustic soda lye, g gfl gg zgg g z g gy figi 3 2 33 322133: into hydrochloric acid. The diazotization being complete, the diazo compound is coupled with $23 g igfig dunng severil hours 15.1 parts of 1-aoetylamino-2-hydroxybenzene in r S phuric After the presence of 13 3 parts of 307 caustic soda lye monoazo dyestufli possessing the probable forare dissolved in water in the presence of 13.3 parts of 30% caustic soda lye and '7 parts of sodium nitrite are added thereto. This solution is allowed to run, under good stirring and cooling,

sodium carbonate and water. The disazo dyestufi isthen salted out in the warmth and filtered. For the purpose of saponification it is boiled during severalhours with 1000 parts of water, 500 parts of ethanol and 100 parts of concentrated sulphuric. acid and filtered after having been cooled down. For furtherdiazotization the disazo dyestuff is dissolved in water in presence of caus- V .tic soda lye, then '7 parts of sodium nitrite are is filtered and Washed Wlth Water- It is then (115- addedthereto and the solution is allowed to run,

solved in caustic soda lye and water, treated with e 7 parts or sodium nitrite and the solution thus $135iffgggfififl fiilfi iffif Obtained 15 allowed to run, under thQmugmY pled with 11 parts of resorcinol dissolved in a so- 11118 8411d t 10W pe ature. into dlluted'hyd odium carbonate solution. -After coupling the chloric acid. When the diazotization hasflnished, t d t fi is Salted 01min the Warm; and the product is coupled with 11 parts or resorcinol coupled in a sodium carbonate solution with the dissolved in a. sodium carbonate solution. The intermediate compound prepared from 18.4 parts disazo dyestufi is then precipitated by means of of benzidine and 13.8 parts of salicylic acid. hydrochloric acid, redissolved in water in pres- After complete coupling the pentakisazo dyestuif ence of sodium carbonate and coupled with the thus obtained is filtered and dried. It possesses intermediate compound prepared from 18.4 parts the probable formula HOaS ndfis), in: the dry st'ate," a dark powderi'dyeing ride; By heating with diluted' sulphuric acidiit I v v on cotton in red-brown shades. After a treatment becomes saponified and afte'r'cooling the same with copper salts the dyeings become violetcan be filtered 01f. The monoazo dyestuffis then brown and possess considerably improved fastness dissolved in water and caustic soda lye and, after properties to washing, light, acids and to alkalis. addition of 7 parts of sodium nitrite, the solution is treated under cooling and good stirrin Example 4 i with hydrochloricacid until .Congo ,acidreaction H has been reached. When the diazotization has 17.3 parts of 1-aminobenzene l sulphonicacid finished,.the mixture is coupled with 11 parts of are diazotized in the usual way and coupled with resorcinol dissolved in a sodium carbonate solu- 15.1 parts of 1-acteylamino-2-hydroxybenzene in tion Thedisazo dyestuff is then precipitated presence of 13.3 parts of caustic soda lye, soby means of hydrochloric acid and sodium chlodium carbonate and water. The dyestuff is then ride and coupled in presence of sodium carbonate precipitated by means of hydrochloric acid and with the intermediate product prepared from saponified by heating the same with diluted sul- 15 18.4 parts of benzidine and 13.8 parts of saliphuric acid. After cooling down the dyestuff is cylic acid. The tetrakisazo dyestufi is then prefiltered; for further diazotization itis dissolved in cipitated in the) warmthby addition of sodium water and caustic soda lye. Then '7 parts of sochloride, filtered and finally dried." It corredium nitrite are added to the solution, the latter sponds to the probable formula r is treated in the cold and under good stirring with and dyes cotton in brownjshades which become diluted hydrochloric acid, until the solution provioletish-brown after a treatment. with copper duces a blue coloration on Congo red paper. salts. This after-treatment improved largely the ,When the-dia zotization has finished, it is coupled fastness' to washing, light, acids and to alkalis.

with 11 parts of resorcinol dissolved in a sodium Example 6 carbonate solution. The disazo'dyestuff thus obv tained is precipitated by means of hydrochloric 16.6 parts of 1-amino-3-acetylamino-bhyacid, filtered and redissolved in water and sodium d oxybenzene are di azotized in the presence of carbonate. It is coupled in the usual manner 6.9 parts of sodium nitrite in a'hydrochloricacid with the intermediate product prepared from 21.2 solutionunder coolin and coupled inpresence parts of 3:3"-tolidine-and 15.2 parts of -1-inethylof sodium carbonatewith 25.6-parts of I-phenyl- 2-hyd-roxy-3-benzoic acid. The tetrakisazo dye- 3-methylpyrazolone-4"-sulphonic acid. The dyestufi'thus obtained is salt-ed out in the heat, stuff is salted out and filtered. .By heating the filtered-and dried, It probably possessesv thesame with diluted sulphuric acid the acetyl group formula is split 0E. The saponified monoazo" dyestufi is and is a dark powder dyeing cotton in redbrown dissolved in water by adding 4 parts of3 0% caus; shades. 'After a treatment withcoppe'rsaltsIth tic, soda lyejthe'n 6. 9 parts of sodium nitrite are dyein s beco vi letish re ow a oss added thereto and the whole is allowed to rung at then a e y p ed ess properties to about 5 0. into diluted hydrochloric acid. After flnf @99 3??? 7 93 5 113 completion fi ot at n of Example 5 i the diazo compound-is coupled with 11 parts: of resorcinol whichhas been dissolved inia, sodium carbonate solution. After lcouplingthe disazo 23.1 parts of 1-acetylamino-2-hydroxybenzene- W W is l ,qi. in Water 5-sulphon ic acid in presences: sodiu rri bicarb'on m the'presence' of wea and coupled ate, water and pyridine. After the coupling has with the intermediate product dirmp 4 finished t pyridine is blown off by means of parts of benzidine and 13.8 parts of salicylic'acid. steam and the monoazo dyestufi is precipitated The tetrakisazo dyestuflz is then salted out, filby means of hydrochloric acid and sodium chlotered and eventually purified byrediss'olving and The diazo compound prepared in the usual way from 22.3 parts of naphthionic acid is coupled with by subsequent precipitation. It corresponds to Further examples are enumerated in the 7101- the probable formula V V r v coon i to I a 1 and is, in the dry state, a dark powder dyeing r 1 cotton in yellowish-brown shades. By an afterlowin table, wherein R stands for resorcinol and treatment with copper salts the dyeings are A stands for the one side coupled monoazo dyelargely improved in their fastnesses to light and stufi obtainable from 1 mole of tetrazotized bento washing. zidine and 1 mole of salicylic acid.

Dyeing on cotton direct after coppered 'HOIS 1 v.

7 H0 N=N 0H; R A red-brown vioIetish-brown.

OH OH 8 N=N V on: no, N=NOH B. -1."; iieiet-bmwmhu--- violetish-dark-brown.

on 011 v 9 N=N 3H,

ILTOQ SOSH N=N- R 4-- A dark-brown.. black-brown.

10 H0sS-O-N= QOH R A; red-brown .i. violetish-bi own.

H NH:

OH: I

12 BOIH N=N --o R A brown Do.

H NH:

13 ONQNHON=NQOH R A.. red-brown violetish-brown. v 0.11 NH; 7 e

14 HOIS- N'H:

Dyeing on cotton I 7 direct after coppered l6 HOaS ON=NQOH "R A brown brown.

NH: a

I a z SOaH --N=N OH R A" vio1etish-brown violetish-brown.

I NH, I v soar! 1s HOaSON==N-QN=N-QOH R A dark brown Do.

Naoor i 1 l9 HO N=N- OE;\TL;NR A brown brown.

SOaNa IP11 OH R A (In Do 20 soon- H00(|J NO: 21 Ho-O-N=N B, A do Do H00? o1 I 22 Ho- N'=N OH=Y R i---- A do Do.

NH: I

What we claim is: zene nucleus I severally carrying a substituent 1. A metallizable .poly'azo dyestuff of the forselected from the class consisting of hydrogen, m v alkyl, nitro, halogen and sulfo.

wherein X represents a member selected from 2, A metallizable polyazo dyestuff of t forthe group consisting of hydrogen and methyl, Y la, t

A I represents a member selected from the group wherein A represents a radical which is free from consisting of hydrogen a y represents diazQotizable amino groups and contains no cara radical which is free from diazotlzable amino ffcapable of coupling, the radical A groups and contains no carbon atoms capable of being; selected fmm the group consisting of radi coupling, the radical A being selected from the 70 group consisting of radicals of the benzene, naphthalene and pyrazolone series, the benzene g r the beilzema coma'mmg one hynucleus I containing one hydroxy group imprdroxy group m ortho'posltlon to the am tho position to the am group which isfiatfth which is at the 3-position, the other free posi- 3-position, the other free positions of the bn- 75 tions of the benzene nucleus I severally ca yi cals of the benzene, naphthalene and pyrazolone 1.1 a substituent selected from the class consisting of hydrogen, alkyl, nitro, halogen and sulfo. e 3. The new metallizable polyazo dyestufi of the formula,

which dyestufi dyes cellulosic fibres in red-brown shades becoming," when after-treated with cop- Der compounds, violet-brown with improved fastness properties.

4. The new metallizable polyazo dyestufi of the formula 12 which dyestuif dyes cellulosic fibres in brown shades becoming, when after-treated with copper compounds, improved in their fastness properties.

Na'N QOH V 5. The new metiiizable polya zo dyestufi' of the formula which dyestufi dyes celluiosic fibres in red-brown shades becoming, when after-treated with copper N=NQoH 13 compounds, brown with improved fastness properties.

I WALTER WEHRLI.

CHARLES PETI'I'JEAN.

REFERENCES crrEn The following references are of record in the file of this patent;

Number Number 14 UNITED STATES PATENTS Name Date Strasburger Mar. 12, 1889 Straub et a1 Dec; 31, 1940 FOREIGN PATENTS Country Date Great Britain 1898 r 

